Interpolymer of diallyl maleate and diethylene glycol maleate phthalate



Patented 'July 27, 1948 INTERPOLYMER OF DIALLYL MALEATE AND DIETHYLENE GLYCOLMALEATE PHTHALATE Gaetano F. DAlelio, Shaker Heights, Ohio, assignor to General Electric Company, a corporation of New York No Drawing.

Original application October 31,

1939, Serial No. 302,174. Divided and this application November 12, 1946, Serial No. 709.193

2 Claims. (Cl. 260-453) This application'is a division of my copending application Serial No. 302,174, filed October 31,

1939, and assigned to the same assignee as the present invention, now Patent No. 2,428,788, issued Oct. 14, 1947.

This invention relates to the production of new materials having valuable and characteristic properties that make them especiall suitable for use in industry, for example in molding, laminating, casting, coating and adhesive applications, and for other purposes. Theinvention is concerned more particularly with compositions of matter comprising an interpolymer (copolymer) or interpolymers of at least one polymerizable esterification product of at least one polyhydrlc alcohol, at least onealpha unsaturated alpha beta polycarboxylic acid and at least one non-ethylenic polycarboxylic acid (hereafter for brevity designated generally as a "non ethylenic modified unsaturated alkyd resin) with at least one polymerizable mono.-

hydric alcohol ester of an alpha unsaturated alpha beta polycarboxylic acid.

A practical advantage accruing from my invention is that it provides new compositions especially adapted for the production of cast or molded massive bodies. The polymerizable nonethylenic-modified unsaturated alkyd resins alone are unsuited, even in the presence of polymerization catalysts such as peroxides, for the preparation of practicallyv useful cast or molded articles of substantial size. If effort be made to prepare commercially useful massive bodies from such alkyd resins alone, even prolonged heat treatment in the presence of a polymerization catalyst usually gives unsuitable materials.

The cast or molded articles often are soft, rubmerizable monohydric alcohol esters of alpha unsaturated alpha beta polycarboxylic acids. I have discovered that advantages in addition to those set forth in the above-identified Nordlander et al. application accrue by internally modifying an unsaturated alkyd'resin with a non-ethylenic polycarboxylic acid and forming a copolymer of the thus modified unsaturated alkyd resin with polymerlzable monohydric alcohol esters of alpha unsaturated alpha beta polycarboxylic acids. Forexample, by forming copolymers with such components'the high exothermic heat given 011 in iorming copolymers with unmodified unsaturated alkyd resins is lessened. As a result, the internal strains in the copolymer are reduced to a minimum and relatively strain-free, tough castings or molded articles can be obtained. Further, due to the lower cost of the common non-ethylenic polycarboxylic acids as compared with the alpha unsaturated alpha beta polycarboxylic acids, substantial economies in producing the finished article are attained. Also, it is extremely diillcult to incorporate a polymerization catalyst into non-ethylenic-modified unsaturated alkyd resins due to their viscous nature. However, as the monohydric alcohol esters of alpha unsaturated alpha beta polycarboxylic acids are good dispersion mediums for the usual polymerization catalysts, there are no difflcuities in incorporating a catalyst into the mixed or dissolved components. The copolymerlzation between the 95 starting materials proceeds satisfactorily, yielding interpolymerization products having properties quite different from the properties of the individual components when polymerized under the same conditions and diiferent from mechanical mixtures of the separately polymerized components.

Another practical advantage'in copolymerizing a polymerizable non-'ethylenic-modified unsaturated alkyd resin with a polymerizable monohydric alcohol ester of an alpha unsaturated alpha beta polycarboxylic acid rather than with other polymerizable materials such, for instance, as styrene, vinyl acetate, methyl methac- .rylate, etc., results from the relatively low vapor pressure of most of these monohydric alcohol esters. This is due to the fact that they are di-esters or, with aconitic acid, tri-esters.

Thus, dimethyl itaconate, which is the lowest the components under heat. The final product stance as coating compositions and binders in the production oi laminated sheets and tapes for use in insulating electrical devices, as well as for other applications,

In carrying the present invention into effect a polymerizable esterlflcation product of a polyhydric alcohol, an alpha unsaturated alpha beta polycarboxylic acid and a non-ethylenic polycarboxylic acid is prepared in accordance with techabove grouping may be any substituted or unsubstituted hydrocarbon radical derived from a monohydric alcohol, that is, an organic compound having one and only one esterifiable hydroxy radical. In other words, R and R of the above grouping may be any normal or branched chain, saturated or unsaturated alkyl radicals with or without substituent groupings, or aryl radicals,

polynuclear aromatic radicals, hydrocyclic radicals etc., and they may be the same or diflerent. The solubility or compatibility of the nonethylenic-modifled unsaturated alkyd resin with the nique now well known to those skilled in the alkyd resin art. Any polyhydric alcoh'ol containing at least two esteriflable aliphatic hydroxy groups, or mixtures of such alcohols. may be used in preparing the non-ethylenic-modifled unsaturated alkyd resin. Examples of such polyhydric alcohols are ethylene glycol, (11-, triand tetra-ethylene glycols, propylene glycol, trlmethylene glycol, thiodiglycol, glycerine, pentaerythritol, etc. Any alpha unsaturated alpha beta polycarboxylic acid, or mixtures of such acids, may be reacted with the polyhydric alcohol or alcohols to form the unsaturated alkyd resin. Examples of such polycarboxylic acids are maleic, monohalomaleic, iumarlc, monohalofumaric, citraconic, mesaconic, acetylene dicarboxylic, aconitic, itaconicand its homologues as, for instance, alpha methyl itaconic acid, alpha ethyl itaconic acid, alpha alpha dimethyl itaconic acid, etc.

Various 'non-ethylenic polycarboxylic acids in widely varying amounts may be incorporated into the unsaturated alkyd resin, care being taken that the amount employed isnot such as to render the said alkyd resin non-polymerlzable, or more particularly, non-copolymerizable with the monohydric alcohol ester component 0! the starting mixture or solution. In producing the modified unsaturated alkyd resins used in carrying the present invention into eii'ect, the 'non-ethylenic polycarboxylic acid ordinarily will not exceed substantially 75 mol per cent of the alpha unsaturated alpha beta polycarboxylic acid. Illustrative examples of non-ethylenic polycarboxylic acids which may be used are saturated aliphatic polycarboxylic acids such, for example, as succinic,

monohydric alcohol ester depends, for example, upon the particular polyhydric alcohol used in making the resin and the length of the monoh'ydric alcohol ester radical. Illustrative examples of the monohydric alcohol esters which may be used in carrying the present invention into effect are the symmetrical and unsymmetrical diesters such, for instance, as the dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, dilsobutyl, di-secondary butyl, diamyl, diisoamyl, dihexyl, dioctyl, didecyl, methyl ethyl, methyl propyl, propyl butyl,

.diallyl, dimethallyl, diethallyl, dipropallyl, allyl meth'allyl, allyl ethallyl, dicrotyl, dipropargyl, di- (l-chlorallyl), di-(2-chlorallyl), di-(3-methylallyl) divinyl, di-(2-phenyl allyl), di-(1-phenyl-2- propyn-l-yl), di-(3-methyl-4-nonyn-3-yl), di- (4-methyl-5-decyn-4-yl) dl- (4-methyl-5-undecyn-4-yl), diphenyl, dibenzyl, di-(phenyl ethyl), di-cyclohexyl, di-(methoxy ethyl), di-(ethoxy ethyl), etc., esters of maleic, monoh'alomaleic, fumaric, monohalofumaric, citraconic, mesaconlc, acethylene dicarboxylic, itaconic acidand its homologues as, for instance, alpha methyl itaconic acid, alpha ethyl itaconic acid, alpha alpha dimethyl itaconic acid; etc.; and tri-esters such,

for-instance, as, tri-allyl aconitate, tri-methallyl aconitate, tributyl aconitate, etc.

To achieve copolymerization of the polymerizable non-ethylenic-modifled unsaturated alkyd resin with the polymerlzable monohydric alcohol'ester of alpha unsaturated alpha beta poly- 'carboxylic acid, a solution of the said resin in adipic, glutaric, pimelic, sebacic, azelaic, suberic,

That is, they are polymerizable esters in which th alpha carbon atom is unsaturated and in which the alpha and beta carbon atoms are attached to carbalkoxy groups. R and R or the lyst concentration.

peroxides of the aromatic acid series, e. g., benzoyl peroxide, various per-compounds such as perborates, persultates, perchlorates, etc., aluminum salts such as the halides, e. g., aluminum chloride, etc., organic and inorganic acids such as methacrylic, hydrofluoric, etc., metal compounds of the unsaturated acids as, for instance, cobalt and manganese resinates, linoleates, maleates, etc. Benzoyl peroxide is the preferred catalyst. Anv suitable amount of catalyst may be used, but in general the catalyst concentration will be within the rate of 0.1 to 2.0 per cent by weight 01' the whole.

When rapidity of interpolymerization between the components is of secondary importance, copolymerization may be effected merely under the influence of heat, light, or heat and light and in the absence of an accelerator of polymerization. The rate of copolymerization .and the properties 01 the final product vary with the time, temperature and, if a catalyst is used, also with the cata- Copolymerization may be effected at from room temperature (20 to 30 C.)

to temperatures above 100 C., for example about 130 C., but ordinarily I use temperatures within the range of 60 to 120 C. in causing the mixed components to interpolymerize.

In order that those skilled in the art better may understand how the present invention may be carried into eilect the following examples are given by way of illustration. All parts are by weight. Reference is first made to the comp nents, and prc ortions thereof, used in the preparation of the non-ethylenic-modified unsaturated alkyd resins. These resins (identified by letter designations) were copolymerized for varyin periods of time with monohydric alcohol esters of alpha unsaturated alpha beta polycarboxylic acids, specifically diallyl itaconate and diallyl maleate, using 1 per cent by weight of the mixed components of benzoyl peroxide. as an accelerator of polymerization, to form cured interpolymerization products of such resistance to heat and ordinary solvents that they properly may be described as insoluble and infusible compositions,

Non-ethylenic-modifled unsaturated alkyl resin Resin Composition A ethylene glycol (02.05 parts), itaconic acid (32.51 parts) and phthalic anhydride (111.03 ports).

B glycerino (20 parts), itnconic acid (20 parts) and phthalie anhydrido (11 arts).

C diethylcne glyco (20 parts), iiaeonic acid (18.2 parts) and succinic acid (7.08 parts D ethylene glycol (20 parts), mnlcic anhydride (29.4 parts) and suceinic acid (3.3 parts).

E diethylcne lycol (30.3 parts), maleic anyhdrido (13.2

parts) an phthalic anhydridc 21.7 parts) F glyccrine (25.76 parts), malcic an ydride (13.73 parts) and phthalic anhydridc (20.72 parts) CopOlymers of non-ethyZenic-modifled unsaturated alkyd resins with monohydric alcohol es- 7 ters of alpha unsaturated alpha beta polycarboxylic acids Characteristics of Copolymer after Monohydric Resin Parts Parts Interpolymerizution at 10 o. for

stated Time 00 diallylitaconatc... 10 hard, clear after 24 hours 10 do 00 Do 00 do 10 Do 90 l0 10 Do 90 do 10 Do 90 diethylitaconatti" 10 Do 80 dialiylitaconatc... 20 Soft, slightly turbid, gel-like after 24 hours.

A 90 diallyl ma1cato. 10 hard, clear after 96 hours B 90 .do 10 D0.

0 90 do 10 hard, clear alter 120 hours.

D 90 .do 10 hard, clear alter 204 hours.

E 80 do 20 hard, clear after 24 hours.

F 80 ..do 20 fairly hard, clear after 96 hours.

In certain cases, instead of copolymerizing a single non-ethylenic-modifled unsaturated alkyd resin, I may copolymerize a plurality of the said esters with a single alkyd resin of thekind with which this invention is concerned or with a plurality of such resins. In this way it is possible to obtain a composition comprising a mixture of interpolymers best adapted tomeet a. particular service application.

It also will be understood that my invention is not limited to the particular proportions of the individual components given in the above illustrative examples, and that the proportions may be varied depending upon the particular properties desired in the interpolymer. Thus, the incorporation into a polymerizable non-ethylenlcmodifiedunsaturated alkyd resin of as little as 3 or 4 per cent of certain polymerizable monohydric alcohol esters, more particularly unsaturated monohydric alcohol esters of alpha unsaturated alpha beta polycarboxylic acids, e. g., diallyl itaconate, yields copolymers of improved properties as compared with such .alkyd resin which has been polymerized in the absence of such ester. However, in many cases it is desirable, particularly where more fluid compositions are required, that the polymerizable monohydric alcohol ester constitute a higher percentage proportion of the initial mixture, say 30 to 70 per cent by weight thereof. Depending upon the particular purpose for which the material is to be used, the percentage proportions of the initial components generally are within the range of 10 to per cent of the monohydric alcohol ester to 90 to 10 per cent of the alkyd resin.

The interpolymerization products of this invention have a. wide range of properties. Depending upon the particular starting components, the particular proportions thereof, the nature of the polymerization influences and the extent of the interpolymenization, they vary from soft, flexible,

may be so used. For coating and impregnating applications where the presence of a small amount of solvent in the cured composition is not objectionable, the mixed polymerizable materials may be diluted with volatile or non-volatile solvents to viscosities best adapted to meet .the particular service application, and then may be copolymerized after application of the solution to the particular article to be coated or impregnated. By suitable selection of the starting materials and the conditions of interpolymerization, interpolymers can be obtained in an insoluble, infusible state practically resistant to the destructive effect of other chemical bodies such as acids, bases, solvents and the like.

These new interpolymers may be used alone or with fillers or other modifying agents, for example in casting and molding applications, as adhesives, impregnants and surface coating materials. They may be used as impregnan ts for many porous bodies, such as cork, pottery, felts, or fabricated bodies with interstices, e. g., the windings of electrical coils, netted fiber, interwoven fibrous materials, etc. They also may be used for protectively coating impervious anticles such as metals, or for coating or coating and impregnating articles such as paper, wood, cloth, glass fibers, concrete, synthetic boards, etc. They also may be employed in the production oi. wire enamels. The mixed com ponents or partial interpolymers thereof, with or' without modifying agents, may be cast and molded under heat or under heat and pressure. They also may be molded by injection. extrusion or compression molding technique whereby they are heatand pressure-hardened to yield molded articles of 'n'ianufacture i'or various industrial.

household and novelty uses.

[What I claim as new and desire to secure by Letters Patent 01 the United States is:

1. A composition comprising the product 01' polymerization of a. polymerizable mixture containing diailyi maleatc and diethylene glycol maieete phthala-te, said materials being copolymerizable.

2. The method of producing new synthetic compositions which comprises polymerizing a polymerizable composition comprising (1) diallyl' maleate. (2) diethylene glycol maleate phthulate and (3) a. catalyst for accelerating the copoiy- 10 merization of (1) and (2).

ammo r. DALELIO. 

